EP3331979B1 - Wc ball and wc cage - Google Patents

Description

The present invention is in the field of toilet blocks and relates to a toilet block which consists of at least a mass and a core. The invention also relates to a toilet basket comprising a toilet block according to the invention.

Toilet blocks with two masses are known, for example from EP0791047 B1 . A toilet block is described there in which one mass is at least partially enclosed by another mass. Since both masses have a common active ingredient in different concentrations, there is a change in the concentration of the active ingredient when it is rinsed off and when it is completely transferred to the inner mass. However, this change is abrupt, and continuous change is not possible with this technique without a great deal of effort.

From the DE102008028138A1 Coated toilet blocks are known; the compositions of the toilet block and its coating are separate. When used for the first time, for example when flushing for the first time, no active ingredient is released from the toilet block into the flushing water, but rather from its coating. This allows the visual properties of the toilet block to be adjusted. Continues to see WO2010018006 proposes to coat the toilet blocks in order to adjust their optical properties.

From the WO2006070209 Cylindrical toilet blocks are known that have a core. These are used primarily as in-tank cleaning blocks and are intended to be permanently submerged in water.

In the WO2012062914 Multi-layered toilet blocks or bricks are described, whereby the different layers can have different effects.

Out of US6376442B1 discloses a toilet cleaning block with a perceived approximately constant intensity of scent throughout the life of the block, comprising an inner region with an internal scent and an outer region with an external scent that is different from the internal scent.

The EP1553162A1 discloses a toilet cleaning and freshening block comprising a solid phase and a gel phase, the gel phase containing perfume and disposed on the surface of the solid phase.

In WO2006070209A1 A toilet cleaning block consists of two parts, the recipes of which are such that one part has a significantly shorter service life than the other part. The part that dissolves faster can introduce a different active ingredient into the toilet bowl or have a stronger effect, e.g. B. in the form of foam or smell, exert on the user. The EP0791047A1 shows pieces of cleaning agent which consist of at least two differently composed masses, one of the masses being at least partially enclosed by the other mass or masses and the enclosed mass containing an active ingredient of a higher concentration than the enclosing mass.

An essential feature of the previously known embodiments of the prior art is that the transition between the layers is abrupt, this is particularly the case if the transition is intended to represent a consumption indicator. No solution has yet been found to realize a continuous change in the delivery of active ingredients.

This problem is solved by a toilet block according to claim 1. The present invention relates to a toilet block which consists of at least one shell and one core. The jacket comprises a first composition and the core comprises a second composition.

The first and second compositions differ by at least one of the following features: different active ingredients, different concentrations of the same active ingredient or a different viscosity. The mantle partially encloses the core mass. The core projects, on at least one side of the toilet block, as a pole up to the surface of the toilet block and is thereby exposed. Preferably, the course of the core in the toilet block is designed in such a way that the surface of the exposed area changes when the surface of the toilet block is evenly removed.

With a wide variety of geometric external shapes of the toilet block, it is possible to simultaneously release active ingredients from the shell and from the core into the flush from the start. The release ratio of active ingredients from the jacket and from the core can be specifically adjusted to the number of flushes. In particular, the delivery ratio can be adjusted so that it changes continuously with the number of flushes. It is preferred that the change be continuous.

Preferably, the initial position on the undissolved toilet block is decisive for the change in the surface of the exposed area of the core and thus the change in the active ingredient composition released into the flush. In other words, the starting point is, preferably, the undissolved toilet block in its original, unused condition. For the purposes of the invention, exposed means the exposed surface.

External, for example full-surface, coatings on the toilet block, which, for example, ensure that the unused toilet block shines, can also be provided. Such layers are generally very thin, so that they are dissolved during the first rinses, preferably during the first three rinses, particularly preferably during the first rinse. Accordingly, the actual release of active ingredients into the rinse water only begins after this outer coating has dissolved. Therefore, for the present invention, the starting point for the undissolved toilet block is understood to be the toilet block without this outer coating.

In one embodiment of the invention it is provided that the surface of the exposed surface of the core increases as the surface of the toilet block is uniformly removed in the course of continued use.

In a particularly preferred embodiment of the invention, it is provided that the surface of the exposed surface of the core is reduced as the surface of the toilet block is uniformly removed. This makes it possible, for example, to reduce the release of an active ingredient that is to be released from the core in such a way that a consumer can perceive the reduction as a consumption indicator.

It is preferred that the area ratio of the exposed surface of the core to the exposed surface of the shell in the undissolved WC stone is between 5% and 67%, particularly preferably between 10% and 38%.

A complete coverage of the toilet block in the unused original state of the toilet block by the core (99%-100% coverage) or by the jacket is also possible, but less preferred. Because of the entire coverage, with the undissolved toilet block, only one composition can initially be released.

It is preferred that after partial consumption of the toilet block, the area ratio of the exposed surface of the core to the exposed surface of the jacket is between 1:3 to 1:1.

It is further preferred that the toilet block comprises a second pole, which projects to the surface on the side of the toilet block opposite the first pole and is thereby exposed.

Preferably at least one, preferably the middle core section is designed as a cylindrical segment. Particularly for two-pole toilet bricks, the core can be produced with a distribution that is essentially symmetrical to the two poles, provided the middle section is cylindrical.

It is also preferred that the first pole and the second pole are connected by a strand. A one-piece core design is preferred. This results in a better time course of the release of the active ingredient while the toilet block is being used.

In the case of two-pole toilet blocks, especially those that are connected by a strand, it is preferred that the cross-sectional shape of the core between the first pole and the second pole has a cross-sectional reduction.

According to a preferred embodiment of the invention, in particular combined with two-pole toilet blocks, it is provided that the jacket surrounds the core in a ring shape. This means that the core can extend through the center of the ring and be designed to be unfolded on one side as the first and second pole.

In an alternative embodiment of the invention, the cross-sectional shape of the core between the first pole and the second pole has an enlarged cross-section.

The toilet block is spherical. The sphericity is preferably between 0.8 and 1, ie essentially spherical, particularly preferably between 0.85 and 1, very particularly preferably between 0.9 and 1. A particularly preferred embodiment of the invention provides a toilet basket that has at least 2, preferably at least 3 spherical Includes toilet blocks that are arranged in a row, it being further preferred that the poles of the toilet blocks are in a random arrangement. Random arrangement means that the toilet blocks included in the toilet block arrangement have different pole orientations. Such a toilet basket is cheaper to produce because it is not necessary to pre-orientate the toilet blocks. It was found that with spherical toilet blocks according to the invention, pre-orientation is not necessary to deliver the desired delivery ratio with the number of flushes. Of course, the toilet blocks can also be oriented if a certain aesthetic shape is desired, especially if the core and the shell have different colors.

wobei Vp das Volumen des Körpers und Ap seine Oberfläche bezeichnet Durch die nahezu ideale kugelförmige Ausbildung des WC-Steins wird ein gleichmäßiges Abspülen des WC-Reinigungsblocks in der Art bewirkt, dass der WC-Stein seine Kugelform auch während bzw. nach den Abspülvorgängen und einem entsprechendem Abtrag des WC-Reinigungsblocks im Wesentlichen beibehält.The sphericity Ψ of a body K is the ratio of the surface area of the body to the surface area of a sphere of the same volume: $$\mathrm{\Psi }=\frac{{\mathrm{<figure-callout\; id="1"\; label="\pi "\; filenames="imgf0001.png,imgf0002.png"\; state="\{\{state\}\}">\pi </figure-callout>}}^{\frac{1}{3}}{\left(6{\mathrm{<figure-callout\; id="2"\; label="v\; p"\; filenames="imgf0001.png,imgf0002.png"\; state="\{\{state\}\}">v</figure-callout>}}_p\right)}^{\frac{2}{3}}}{A_p},$$

where Vp denotes the volume of the body and Ap denotes its surface. The almost ideal spherical design of the toilet block ensures that the toilet cleaning block is flushed evenly in such a way that the toilet block retains its spherical shape even during or after the flushing processes and a corresponding removal of the toilet cleaning block is essentially retained.

The diameter of the spherical toilet block is preferably between 1 mm and 10 cm, preferably between 5 mm and 5 cm, particularly preferably between 1 cm and 3 cm.

1. a) Mischen der Inhaltsstoffe für die Kernzusammensetzung, und
   Mischen der Inhaltsstoffe für die Mantelzusammensetzung,
2. b) Co-Extrusion der mindestens zwei Gemische,
3. c) Schneiden des extrudierten Strangs in Portionsstücke einer definierten Masse,
4. d) Verformung zu rotationssymmetrischen Körpern, so dass der Kern auf mindestens einer Seite des WC-Steins, als einen Pol bis zur Oberfläche ragt und dabei exponiert ist.

Yet another subject of the invention is an associated method for producing a rotationally symmetrical toilet cleaning block, comprising the steps

1. a) mixing the ingredients for the core composition, and
   mixing the ingredients for the coat composition,
2. b) co-extrusion of the at least two mixtures,
3. c) cutting the extruded strand into portion pieces of a defined mass,
4. d) Deformation into rotationally symmetrical bodies, so that the core protrudes as a pole to the surface on at least one side of the toilet block and is thereby exposed.

The deformation d) preferably takes place in a ball rolling machine or a press. A preferred ball rolling machine is one with three rotating molds or rollers into which the strand can be placed and, by reducing the distance between the rollers, the strand is cut through the roller mold and formed into a ball. Because the strand section is pressed into a spherical space with identical volumes, the desired final geometry according to the invention is achieved.

Steps a) and b) can also be combined, i.e. mixing the ingredients in the extruder. The process steps may take place at different temperatures, so that heating or cooling steps can be interposed between the steps. These are at the discretion of the specialist.

In a preferred embodiment, a further process step is carried out following one of steps b) or c), in which the extruded strand is provided with a lubricant. For this purpose, a sponge in the form of an impeller, which is permanently mixed with the lubricant, is guided over the extruded strand in such a way that the surface is completely or partially, preferably 10 to 40%, covered with lubricant. The addition of the lubricant improves the subsequent ball forming. Suitable lubricants are, in particular, substances which are used, for example, as surfactants or rinsing regulators in recipes according to the invention. Particular preference is given to using a lubricant selected from the group comprising dipropylene glycol, paraffins, nonionic surfactants, polyethylene glycols and mixtures thereof, in particular dipropylene glycol.

• e) Bereitstellung von Kunststoffhalterung, vorzugsweise durch Spritzgussverfahren;
• f) Einlegen der WC-Steine in die Kunststoffhalterung;
• g) Verschließen der Kunststoffhalterung.

The process for producing the toilet basket includes steps a) to d) described above and further includes:

• e) provision of plastic holder, preferably by injection molding;
• f) Inserting the toilet blocks into the plastic holder;
• g) Closing the plastic holder.

Preferably, the toilet blocks are temporarily stored in a container between steps d) and f). The container forms a kind of buffer, and this means that the production of the toilet blocks can be decoupled from the production of the toilet baskets. Preferably, the toilet blocks used in the baskets come from at least two containers, the containers having stored toilet blocks with different compositions. This means that a toilet basket can be produced that can release active ingredients from different toilet blocks with different compositions.

composition

The first and second compositions preferably differ by at least containing different active ingredients and/or by a different concentration of the same active ingredient, the active ingredients concerned preferably being selected from the following list: perfume, surfactant(s), dyes, rinsing regulators, Bleach, builder, acid or base, antimicrobial agents, polymers. It is particularly preferred that the active ingredients concerned are selected from at least one of: perfume, surfactant(s), dyes. In the case of a toilet block in which the first and second compositions differ in a different concentration of the same active ingredient, it is preferred that the core has a higher concentration of this active ingredient. Preferably, the higher concentration in the core is at least 0.5% by weight greater than in the shell. Furthermore, it is preferred that the active ingredient is present in the core with a higher concentration of at least 1% by weight to 10% by weight than the concentration in the jacket. The weight % information is always in relation to the overall composition of 100%. A higher concentration of x% by weight means x percentage points more.

The toilet basket according to the invention with a toilet block can also be used in a method for cleaning and / or scenting and / or disinfecting flush toilets in such a way that the toilet basket filled with the toilet block is hung in the toilet bowl and When you flush the toilet, dissolved ingredients in the toilet block get into the flushing water and can develop their cleaning and/or fragrant and/or disinfecting effect there. Yet another subject of the invention is therefore a method for cleaning and/or scenting and/or disinfecting flush toilets using a toilet basket according to the invention with a toilet block.

Substances that also serve as ingredients in cosmetic products may be referred to below according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds have an INCI name in English, herbal ingredients are only listed in Latin according to Linnaeus, so-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The INCI designations are dem International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997), published by The Cosmetic, Toiletry, and Fragrance Association (CTFA), 1101 17th Street, NW, Suite 300, Washington, DC 20036, USA , is published and contains more than 9,000 INCI names as well as references to more than 37,000 trade names and technical names including the associated distributors from over 31 countries. The International Cosmetic Ingredient Dictionary and Handbook assigns the ingredients one or more chemical classes ( Chemical Classes ), for example Polymeric Ethers , and one or more functions ( Functions ), for example Surfactants - Cleansing Agents , which it in turn explains in more detail and refers to below may also be referred to.

The indication CAS means that the following sequence of numbers is a designation from the Chemical Abstracts Service .

In the context of the present invention, fatty acids or fatty alcohols or their derivatives - unless otherwise stated - represent branched or unbranched carboxylic acids or alcohols or their derivatives with preferably 6 to 22 carbon atoms, in particular 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms, most preferably 12 to 16 carbon atoms, for example 12 to 14 carbon atoms. The former are preferred for ecological reasons, in particular because of their plant base as based on renewable raw materials, but without the teaching according to the invention applying to them restrict. In particular, the oxo alcohols or their derivatives obtainable, for example, by Roelen's oxo synthesis, preferably have 7 to 19 carbon atoms, in particular 9 to 19 carbon atoms, particularly preferably 9 to 17 carbon atoms, extremely preferably 11 to 15 carbon atoms, for example 9 to 11 , 12 to 15 or 13 to 15 carbon atoms, can be used accordingly.

Perfume

The compositions each contain one or more fragrances, preferably in an amount of 0.01 to 15% by weight, in particular 1 to 11% by weight, particularly preferably 1 to 8% by weight. Preferably, the concentration in the shell is between 1% by weight and 3% by weight and the concentration in the core is at least 0.5% by weight greater, particularly preferably between 1.5% by weight and 8% by weight.

D-Limonene can be included as a perfume component. In a particularly preferred embodiment, the toilet cleaning block according to the invention contains a perfume made from essential oils (also referred to as essential oils). As such, for example, pine, citrus, jasmine, patchouly, rose or ylang-ylang oil can be used in the context of this invention. Also suitable are clary sage oil, chamomile oil, lavender oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

In order to be perceivable, a fragrance must be volatile; in addition to the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. Most fragrances have molecular weights of up to around 200 Daltons, while molecular weights of 300 Daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume composed of several fragrances changes during evaporation, with the odor impressions being divided into “top note”, “middle note” (body) and “base note”. " (end note or dry out).

Adhesive fragrances that can advantageously be used in the perfume oils in the context of the present invention are, for example, the essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, champaca flower oil, noble fir oil, noble fir cone oil, elemi oil, eucalyptus oil, fennel oil, spruce almond oil, galbanum oil, geranium oil, Gingergrass oil, Guaiac wood oil, Gurjun balsam oil, Helichrysum oil, Ho oil, Ginger oil, Iris oil, Kajeput oil, Calamus oil, Chamomile oil, Camphor oil, Kanaga oil, Cardamom oil, Cassia oil, Pine needle oil, Kopaïva balsam oil, Coriander oil, Spearmint oil, Caraway oil, Cumin oil, Lemongrass oil, Musk seed oil, Myrrh oil, Cloves oil, Neroli oil, Niaouli oil, Olibanum oil, Origanum oil, Palmarosa oil, Patchouli oil, Peru balsam oil, Petitgrain oil, Pepper oil, Peppermint oil, Allspice oil, Pine oil, Rose oil, Rosemary oil, Sandalwood oil, Celery oil, Star anise oil, Thuja oil, Thyme oil, Verbena oil, Vetiver oil, Juniper berry oil, Wormwood oil, Wintergreen oil, Ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil and cypress oil.

But the higher-boiling or solid fragrances of natural or synthetic origin can also advantageously be used as adhesive fragrances or fragrance mixtures in the perfume oils within the scope of the present invention. These compounds include the following compounds and mixtures of these: ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anise alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, borneol, bornyl acetate, α-bromostyrene, n -Decylaldehyde, n-dodecyl-aldehyde, eugenol, eugenolmethylether, eucalyptol, fernchon, fennchyl acetate, geranylacetate, geranylformiat, heliotropine, heptincarboxicemethylester, heptaldehyde, hydrochinon-di-methylether, hydroxymaldgehyde, hydrohyde Droxyzimmal alcohol, Indol, Iron, Isoeugenol, Isoeugenolmethyl ether, isosafrol , jasmone, camphor, karvakrol, karvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilic acid methyl ester, p-methyl acetophenone, methyl chavicol, p-methyl quinoline, methyl β-naphthyl ketone, methyl n-nonylacetaldehyde , methyl n-nonyl ketone, muskone, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, nitrobenzene, n-nonyl aldehyde, nonyl alcohol, n-octyl aldehyde, p-oxy-acetophenone, pentadecanolide, β-phenyl ethyl alcohol, phenylacetaldehyde dimethyl acetal, phenylacetic acid , pulegone, safrole, salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester, salicylic acid cyclohexyl ester, santalol, skatole, terpineol, thymene, thymol, γ-undelactone, vaniline, veratrumaldehyde, cinnamaldehyde, cinnamic alcohol, cinnamic acid, cinnamic acid ethyl ester, cinnamic acid benzyl ester.

The more volatile fragrances that can be used advantageously in the perfume oil in the context of the present invention include, in particular, the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione _, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.

Surfactants

The toilet block according to the invention contains at least one nonionic surfactant, which contains a C _12-22 fatty alcohol akoxylate with a degree of ethoxylation of 12 to 28, as well as at least one alkyl benzene sulfonate and at least one olefin sulfonate. In addition, other surfactants may be included.

When it comes to alkyl benzene sulfonates, preference is given to those with about 12 carbon atoms in the alkyl part, such as linear sodium C10-13 alkyl benzene sulfonate. Preferred olefin sulfonates have a carbon chain length of 14 to 16. The toilet cleaning block according to the invention preferably contains 10 to 70% by weight, preferably 20 to 65% by weight, particularly preferably 20 to 30% by weight of alkyl benzene sulfonate and preferably 10 to 30% by weight, preferably 15 to 30% by weight, particularly preferably 15 to 25% by weight of olefin sulfonate.

Non-ionic surfactants

In addition to the C _12-22 fatty alcohol axoxylate with a degree of ethoxylation of 12 to 28, other nonionic surfactants may be included. Other suitable nonionic surfactants within the scope of the invention can be alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Ethylene oxide/propylene oxide block polymers, fatty acid alkanolamides and fatty acid polyglycol ethers can also be used. Another important class of nonionic surfactants that can be used according to the invention are the polyol surfactants and in particular the glycotensides, such as alkyl polyglycosides and fatty acid glucamides. The alkyl polyglycosides, in particular the alkyl polyglucosides, and especially the fatty alcohol alkoxylates (fatty alcohol polyglycol ethers) are particularly preferred.

Preferred fatty alcohol alkoxylates are unbranched or branched, saturated or unsaturated C _8-22 alcohols with a degree of alkoxylation of up to 30, preferably ethoxylated C _12-22 fatty alcohols with a degree of ethoxylation of less as 30, preferably 12 to 28, in particular 20 to 28, particularly preferably 25, for example C _16-18 fatty alcohol ethoxylates with 25 EO.

Alkyl polyglycosides are surfactants that can be obtained by reacting sugars and alcohols using the relevant methods of preparative organic chemistry, which, depending on the type of production, result in a mixture of monoalkylated, oligomeric or polymeric sugars. Preferred alkyl polyglycosides are the alkyl polyglucosides, whereby the alcohol is particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched C ₈ to C ₁₈ alkyl chains and the degree of oligomerization (DP) of the sugars is between 1 and 10, preferably 1 to 6. in particular 1.1 to 3, most preferably 1.1 to 1.7, for example C _8-10 alkyl-1,5-glucoside (DP of 1.5).

Fatty alcohol ethoxylates are preferably used in amounts of up to 20% by weight, particularly preferably 4 to 12% by weight, particularly preferably 7 to 9% by weight. In addition, other nonionic surfactants, such as fatty acid monoalkanolamides and/or alkyl polyglycosides, can be contained in amounts of up to 10% by weight.

Other anionic surfactants

Other anionic surfactants in the toilet block according to the invention can be aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkane sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin sulfonates. Also usable within the scope of the present invention are fatty acid cyanamides, sulfosuccinates (sulfosuccinic acid esters), in particular Sulfobernsteinic acid and -ddi -c ₈ -c ₁₈ -Alkylester, sulfosuccinamate, sulfosuccinamide, fatty acid ethionate, acylaminoalkansulfonate (fatty acid), fatty acid cosinates, ether carbons acids and alkyl Esalts, acylglutamate, monoglyceriddisulfate and alkyl ether of the glycerin indic sulfate.

In the context of the present invention, preference is given to the fatty alcohol sulfates and/or fatty alcohol ether sulfates, in particular the fatty alcohol sulfates. Fatty alcohol sulfates are products of sulfation reactions on corresponding alcohols, while fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. The person skilled in the art generally understands alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the sense of the present invention preferably with longer-chain alcohols. As a rule, n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions, produce a complex mixture of addition products with different degrees of ethoxylation. A further embodiment of the alkoxylation consists in the use of mixtures of alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Preferred fatty alcohol ether sulfates are the sulfates of lower ethoxylated fatty alcohols with 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1.3 EO.

The anionic surfactants are preferably used as sodium salts, but can also be present as other alkali or alkaline earth metal salts, for example magnesium salts, as well as in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form their corresponding acid, e.g. dodecylbenzenesulfonic acid.

In addition to the surfactant types mentioned so far, the agent according to the invention can also contain cationic surfactants and/or amphoteric surfactants.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ )(R ^iv )(R ^v )N ⁺ CH ₂ COO ^- , in which R ⁱⁱⁱ is an alkyl radical with 8 to 25, preferably 10 to 21, carbon atoms, optionally interrupted by heteroatoms or heteroatom groups, and R ^iv and R ^v represent similar or different alkyl radicals with 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -alkyldimethylcarboxymethylbetaine and C ₁₁ -C ₁₇ -alkylamidopropyldimethylcarboxymethylbetaine.

Suitable ^cationic surfactants include the quaternary ammonium ^compounds of ^the formula (R ^vi )(R ^vii )(R ^viii )(R ^ix )N ⁺ short-chain ^, alkyl radicals and

Other ingredients

In addition to the components mentioned so far, the toilet block according to the invention can contain other ingredients that are usually used in toilet blocks, preferably selected from Group comprising acids, bases, salts, thickeners, antimicrobial active ingredients, preservatives, complexing agents, polymers, dyes, fragrances, perfume boosters, fillers, builders, bleaching agents, corrosion inhibitors, rinsing regulators, enzymes, microorganisms, active ingredients for biofilm removal, active ingredients for inhibiting limescale deposits, active ingredients to reduce dirt adhesion, active ingredients to improve processability, active ingredients to reduce stickiness and mixtures thereof. Overall, no more than 60% by weight of other ingredients should be contained, preferably 0.01 to 60% by weight, in particular 0.2 to 15% by weight.

acids

Toilet blocks according to the invention can contain one or more acids and/or their salts to increase the cleaning performance against lime and urine scale. The acids are preferably produced from renewable raw materials. Suitable acids are therefore particularly organic acids such as formic acid, acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid and mixtures thereof. In addition, the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid or amidosulfonic acid or mixtures thereof can also be used. The acids and/or their salts are particularly preferably selected from the group comprising citric acid, lactic acid, formic acid, their salts and mixtures thereof. They are preferably used in amounts of 0.01 to 10% by weight, particularly preferably 0.2 to 5% by weight.

In addition, in a preferred embodiment, the composition contains inorganic salts, preferably alkali or alkaline earth metal salts, in particular carbonates, sulfates, halides or phosphates and mixtures thereof. Sodium sulfate and/or sodium carbonate are particularly preferably used. Sodium sulfate can be present in an amount of up to 60% by weight, preferably 0.01 to 60% by weight, particularly preferably 20 to 60% by weight, in particular 35 to 55% by weight. Sodium carbonate and other salts can be present in an amount of up to 30% by weight, preferably up to 10% by weight, particularly preferably up to 5% by weight.

bases

Alkalis can also be contained in compositions according to the invention. The bases used in compositions according to the invention are preferably those from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide. In addition, ammonia and/or alkanolamines with up to 9 carbon atoms in the molecule can also be used, preferably the ethanolamines, in particular monoethanolamine.

Antimicrobial agents

Disinfection and sanitation represent a special form of cleaning. In a corresponding special embodiment of the invention, the toilet cleaning block therefore contains one or more antimicrobial active ingredients, preferably in an amount of 0.01 to 1% by weight, preferably 0. 02 to 0.8% by weight, in particular 0.05 to 0.5% by weight, particularly preferably 0.1 to 0.3% by weight, most preferably 0.2% by weight.

The terms disinfection, sanitation, antimicrobial effect and antimicrobial active ingredient have the usual meaning in the context of the teaching according to the invention. While disinfection in the narrower sense of medical practice means the killing of - theoretically all - infectious germs, sanitation is understood to mean the elimination as far as possible of all - including saprophytic germs that are normally harmless to humans. The extent of disinfection or sanitation depends on the antimicrobial effect of the composition used, which decreases as the content of antimicrobial active ingredient decreases or the composition is increasingly diluted for use.

Suitable according to the invention are, for example, antimicrobial active ingredients from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and the like Derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, lodo-2-propynyl-butyl-carbamate, iodine, iodophors, active chlorine compounds and peroxides. Preferred antimicrobial active ingredients are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2- Benzyl-4-chlorophenol, 2,2'-methylene-bis-(6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N-(4-chlorophenyl)-N-( 3,4-dichlorophenyl)-urea, N,N'-(1,10-decanediyldi-1-pyridinyl-4-ylidene)-bis-(1-octanamine)-dihydrochloride, N,N'-bis-(4- chlorophenyl)-3,12-diimino-2,4,11,13-tetraazatetradecanediimidamide, antimicrobial quaternary surfactants, guanidines and sodium dichloroisocyanurate (DCI, 1,3-dichloro-5H-1,3,5-triazine-2, 4,6-trione sodium salt). Preferred antimicrobial surface-active quaternary compounds contain an ammonium, sulfonium, phosphonium, iodonium or arsonium group. Antimicrobial essential oils can also be used, which at the same time scent the cleaning product. However, particularly preferred antimicrobial active ingredients are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride, peroxo compounds, in particular hydrogen peroxide, alkali metal hypochlorite, sodium dichloroisocyanurate and mixtures thereof.

preservatives

Preservatives can also be contained in toilet cleaning blocks according to the invention. As such, essentially the substances mentioned under the antimicrobial active ingredients can be used.

Complexing agents

Complexing agents ( INCI chelating agents), also called sequestering agents, are ingredients capable of complexing and inactivating metal ions to prevent their adverse effects on the stability or appearance of the agents, such as clouding. On the one hand, it is important to complex the calcium and magnesium ions of water hardness, which are incompatible with numerous ingredients. On the other hand, the complexation of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished products. The complexing agents also support the cleaning effect.

For example, the following complexing agents designated according to INCI are suitable: Aminotrimethylene Phosphonic Acid, Beta-Alanine Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacycloheptane Diphosphonate , Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactaric Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, Pentasodium Triphosphate, Pentetic Acid , Phytic Acid, Potassium Citrate, Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphate, Potassium Trisphosphonomethylamine Oxide, Ribonic Acid, Sodium Chitosan Methylene Phosphonate, Sodium Citrate, Sodium Diethylenetriamine Pentamethylene Phosphonate, Sodium Dihydroxyethylglycinate, Sodium EDTMP, Sodium Gluceptate, Sodium Gluconate, Sodium Glycereth- 1 Polyphosphates, Sodium Hexametaphosphate, Sodium Metaphosphate, Sodium Metasilicate, Sodium Phytate, Sodium Polydimethylglycinophenolsulfonate, Sodium Trimetaphosphate, TEA-EDTA, TEA-Polyphosphate, Tetrahydroxyethyl Ethylenediamine, Tetrahydroxypropyl Ethylenediamine, Tetrapotassium Etidronate, Tetrapotassium Pyrophosphate, Tetrasodium EDTA, Tetrasodium Etidronate, Tetrasodium Pyrophosphate, Tripotassium EDTA, Trisodium Dicarboxymethyl Alaninate, Trisodium EDTA, Trisodium HEDTA, Trisodium NTA and Trisodium Phosphate.

Polymers

The toilet block according to the invention can also contain polymers. These can be used, for example, to reduce limescale formation and the tendency to become dirty again.

Preferred polymers are acrylic polymers, such as those commercially available from Rhodia under the trade name Mirapol.

Fragrances and dyes

The toilet block according to the invention can contain one or more fragrances and/or one or more colorants ( INCI Colorants) as further ingredients. Both water-soluble and oil-soluble dyes can be used as dyes, whereby, on the one hand, compatibility with other ingredients, such as bleaching agents, must be taken into account and, on the other hand, the dye used should not have a substantive effect on the toilet ceramic, even after prolonged exposure. The dyes are preferably contained in an amount of 0.0001 to 0.1% by weight, in particular 0.0005 to 0.05% by weight, particularly preferably 0.001 to 0.01% by weight.

Builders

If necessary, water-soluble and/or water-insoluble builders can be used in the toilet block according to the invention. Water-soluble builders are preferred because they are generally less likely to leave insoluble residues on hard surfaces. Common builders that can be present in the context of the invention are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the citric acid and its salts, the carbonates, phosphates and silicates. Water-insoluble builders include zeolites, which can also be used, as well as mixtures of the aforementioned builder substances.

Bleach

According to the invention, bleaching agents can be added to the cleaning agent. Suitable bleaching agents include peroxides, peracids and/or perborates; hydrogen peroxide is particularly preferred. Sodium hypochlorite, on the other hand, is less suitable for acid-formulated cleaning agents due to the release of toxic chlorine gas vapors, but can be used in alkaline cleaning agents. In addition to the bleach, a bleach activator may also be necessary.

Corrosion inhibitors

Suitable corrosion inhibitors ( Inci corrosion inhibitors) are, for example, the following substances named according to Inci : cyclohexylamine, diammonium phosphate, dilithium oxalate, dimethylamino methylpropanol, dipotassium oxalate, disodium phosphate, disodium pyrophosphere ium tetrapropenyl succinate, hexoxyethyl diethylammonium, phosphate, nitromethane, potassium Silicates, Sodium Aluminate, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrite, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine.

Rinse regulators

The substances known as rinsing regulators primarily serve to control the consumption of the composition during use so that the intended service life is maintained. Suitable regulators are preferably solid long-chain fatty acids, such as stearic acid, but also salts of such fatty acids, fatty acid ethanolamides, such as coconut fatty acid monoethanolamide, or solid polyethylene glycols, such as those with molecular weights between 10,000 and 50,000.

Active ingredients to reduce stickiness

To improve the processability in the production of the toilet block according to the invention, an active ingredient can be added to reduce the stickiness. The addition of dolomite powder or titanium dioxide powder with a fine particle size distribution improves the processing behavior when forming balls and significantly reduces abrasion and stickiness.

The results with such active ingredients are better than with other common measures, for example coating the balls with a lubricant, powdering or coating the forming rollers with Teflon.

Enzymes

The composition may also contain enzymes, preferably proteases, lipases, amylases, hydrolases and/or cellulases. You can add enzymes to the composition according to the invention in any form established in the art. These include solutions of the enzymes, advantageously as concentrated as possible, low in water and/or containing stabilizers. Alternatively, the enzymes can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of core-shell Type in which an enzyme-containing core is covered with a protective layer that is impermeable to water, air and/or chemicals. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers. Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes. Such granules are advantageously low-dust, for example by applying polymeric film formers, and are storage-stable due to the coating.

Furthermore, enzyme stabilizers can be present in enzyme-containing compositions in order to protect an enzyme contained in a composition according to the invention from damage such as inactivation, denaturation or decay, for example due to physical influences, oxidation or proteolytic cleavage. Particularly suitable enzyme stabilizers, depending on the enzyme used, are: benzamidine hydrochloride, borax, Boric acids, boronic acids or their salts or esters, especially derivatives with aromatic groups, such as substituted phenylboronic acids or their salts or esters; Peptide aldehydes (oligopeptides with a reduced C-terminus), amino alcohols such as mono-, di-, triethanol- and propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned; end-capped fatty acid amide alkoxylates; lower aliphatic alcohols and especially polyols, for example glycerin, ethylene glycol, propylene glycol or sorbitol; as well as reducing agents and antioxidants such as sodium sulfite and reducing sugars. Other suitable stabilizers are known from the prior art. Combinations of stabilizers are preferably used, for example the combination of polyols, boric acid and/or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.

), ist vorzugsweise größer als 3, in dem CIE 1976 (L,a*,b*) Farbkoordinatensystem. $${\mathit{\Delta E}}_{\mathit{ab}}^{\ast }=\sqrt{{\left(L_2^{\ast }-L_1^{\ast }\right)}^2+{\left(a_2^{\ast }-a_1^{\ast }\right)}^2+{\left(b_2^{\ast }-b_1^{\ast }\right)}^2}$$

In a particularly preferred embodiment of the invention, the core and jacket have different colors. Furthermore, particularly preferably, the core and jacket each have a homogeneous color. The color difference between the color of the sheath and the core ( ${\mathit{\Delta E}}_{\mathit{away}}^{\ast }$

), is preferably greater than 3, in the CIE 1976 (L,a*,b*) color coordinate system. $${\mathit{\Delta E}}_{\mathit{away}}^{\ast }=\sqrt{{\left({\mathrm{<figure-callout\; id="2"\; label="L"\; filenames="imgf0001.png,imgf0002.png"\; state="\{\{state\}\}">L</figure-callout>}}_2^{\ast }-{\mathrm{<figure-callout\; id="1"\; label="L"\; filenames="imgf0001.png,imgf0002.png"\; state="\{\{state\}\}">L</figure-callout>}}_1^{\ast }\right)}^2+{\left(a_2^{\ast }-a_1^{\ast }\right)}^2+{\left({\mathrm{<figure-callout\; id="2"\; label="b"\; filenames="imgf0001.png,imgf0002.png"\; state="\{\{state\}\}">b</figure-callout>}}_2^{\ast }-{\mathrm{<figure-callout\; id="1"\; label="b"\; filenames="imgf0001.png,imgf0002.png"\; state="\{\{state\}\}">b</figure-callout>}}_1^{\ast }\right)}^2}$$

Alternatively, or additionally, it is preferred that at least one color, preferably both, of the core and the cladding has a chroma of between 20% and 99%, preferably between 30% and 95%.

The color settings according to the invention, individually or preferably combined, greatly improve the consumer's ability to recognize the level of consumption of the toilet block. Because the contrast between the elements makes observation easier.

), vorzugsweise kleiner als 10, vorzugsweise kleiner als 3, in dem CIE 1976 (L,a*,b*) Farbkoordinatensystem. In dem Fall ist es bevorzugt, dass der Kern unterschiedliche Wirkstoffe und/oder unterschiedliche Konzentration eines gleichen Wirkstoffes zum Mantel hat. Dem Verbraucher fällt es nicht auf, wenn der Mantel Verbraucht ist, und es kann den Eindruck entstehen, dass der WC-Stein aus einer einzigen Wirkstoffzusammensetzung besteht. Trotzdem kann z.B. die Funktionalität und die Wirkung des WC-Steins bei starker Abnutzung durch eine geänderte Wirkstoffzusammensetzung des Kerns mindestens teilweise kompensiert werden.In an alternative variant of the invention, the color difference between the color of the jacket and the core ( ${\mathit{\Delta E}}_{\mathit{away}}^{\ast }$

), preferably less than 10, preferably less than 3, in the CIE 1976 (L,a*,b*) color coordinate system. In this case, it is preferred that the core has different active ingredients and/or different concentrations of the same active ingredient to the jacket. The consumer does not notice when the coat is used up and may get the impression that the toilet block consists of a single active ingredient composition. Nevertheless, the functionality and effect of the toilet block in the event of heavy wear can be at least partially compensated for by changing the active ingredient composition of the core.

In this description, the color characteristics refer to the CIE1976 color coordinate system. If an Illuminati is necessary, it will be D65, or a commonly applicable approximation of it.

contraption

The present invention also provides a device comprising a toilet seat as described herein and a holding means for holding the toilet seat to the toilet bowl. Preferably the device is a toilet basket.

Toilet basket

According to the invention, a toilet basket is provided, comprising at least one toilet block according to the invention. The toilet basket can preferably also comprise at least two, particularly preferably at least three toilet blocks according to the invention. The toilet blocks each include at least one pole cap and are arranged regularly or irregularly among themselves. The irregular arrangement is preferred because of the simplified manufacturing method. The regular arrangement is also interesting, especially because of the aesthetic shape, especially when the pole and sheath have a different color. The toilet blocks of the toilet basket are preferably rotationally symmetrical, more preferably spherical.

The toilet basket according to the invention is suitable for dispensing compositions into a toilet bowl. It includes a receptacle to be arranged in the toilet bowl, the receptacle being attachable to the toilet bowl. The receptacle includes a first chamber that holds at least one toilet block. Preferably, the receptacle further comprises a second chamber which accommodates a second toilet block. Preferably, at least one, preferably each, of the toilet blocks is separated from the bottom of the chamber by support means. At least one, preferably all, chambers release the compositions into the toilet bowl when flushing water flows over or through it. The toilet basket is designed in such a way that when flushing water flows over it, the flushing water also comes into contact with the toilet block and the flushing water enriched with active ingredient preparation can escape the toilet basket. For this purpose, for example, inlet and outlet openings, water distribution elements, and other means can be provided. Exemplary embodiments are described using the figures.

Preferably, the toilet basket with the toilet block(s) is closed so that it cannot be opened. Therefore, it is not possible to get to the toilet block(s) without considerable effort and deformation of the toilet basket.

The toilet basket is preferably transparent. This means that a consumer can not only see the color but also the shape of the toilet block.

Figure list

• Fig.1 shows a toilet block according to the invention in a top view of the pole;
• Fig.2 shows a toilet block according to the invention in side view;
• Fig.3 shows a section of the toilet block Fig. 2 towards AA.
• Fig.4 shows a section of the toilet block Fig. 2 towards BB.
• Fig.5 shows a cross section of the pressing process before and after pressing.
• Fig.6 shows a section of a toilet basket comprising 3 toilet blocks.

In a particularly preferred exemplary embodiment, the toilet block 1 comprises the jacket 2 and the core 3. The core 3 forms a pole 4 as shown in the plan view Fig. 1 is visible. In the side view according to Fig. 2 the first pole 4 and the second pole 5 are visible. The core 3 is surrounded by the jacket 2. The casing 2 is ring-shaped, as can be seen in the sectional view AA with, for example, an approximately elliptical section and in the sectional view BB as a circular ring. The pole 4 and/or the pole 5 can/can each be more or less pronounced. This enables a predefined, controlled release of active ingredients over time. The diameter of the segment 6 can also be smaller or larger. Instead of a cylindrical section of the segment 6, it can also have a different geometry.

Comparative example

Toilet blocks were manufactured with the following composition and used as a reference: E1 C _10-13 -lin. Alkylbenzenesulfonate-Na 26 Fatty alcohol sulfate-Na -- C ₁₂ - fatty alcohol sulfate-Na - C _14-16 -olefin sulfonate-Na 18 C _16-18 fatty alcohol ethoxylate 25 EO 8th cellulose -- Trisodium citrate dihydrate 1 Sodium sulfate ad 100 sodium -- C _12-18 fatty acid monoethanolamide -- Sodium silicate -- Perfume 4.5 dye +

The perfume composition used was composed as follows: Dosage % by weight Surname CAS No. 12.16 dipropylene glycol 25265-71-8 8.51 dihydromyrcenol 18479-58-8 7.30 terpineol 8000-41-7 4.86 linalyl acetate 115-95-7 3.65 Lemon oil Messina 84929-31-7 3.65 agrunitrile 51566-62-2 3.65 orange oil sweet ital. 8028-48-6 3.65 otbca 88-41-5 3.65 styrolyl acetate 93-92-5 3.65 linalool 78-70-6 2.43 aldehyde c 08 124-13-0 2.43 alcohol c 08 111-87-5 2.43 allylamyl glycolate 67634-00-8 2.43 benzyl acetate 140-11-4 2.43 hedione 24851-98-7 1.52 linalool oxide 1365-19-1 1.52 lemonile 61792-11-8 1.52 bromeliad 93-18-5 1.52 yara yara 93-04-9 1.52 aldehyde c 10 112-31-2 1.51 aldehyde c 14 so-called 104-67-6 1.50 benzylacetone 2550-26-7 1.50 acedyl 54830-99-8 1.50 propidyl 68912-13-0 1.50 isobornyl acetate 125-12-2 1.50 terpinolene 30 586-62-9 1.50 lilial, lysmeral 80-54-6 1.50 pure citronellol 106-22-9 1.50 geraniol pure 106-24-1 1.50 nerol standard 106-25-2 1.50 phenylethyl alcohol 60-12-8 1.50 geranyl acetate 16409-44-2 1.50 hexylcinnamaldehyde (alpha) 101-86-0 1.50 isoraldine 70 1335-46-2 1.50 jonon beta synth. 14901-07-6 1.50 iso e great 54464-57-2 1.50 ethylene brasilate 105-95-3

The composition was mixed, then extruded into a strand, cut and formed into balls in a mold. The final average of each ball was 25.4 mm.

Example

Toilet blocks according to the invention were produced as follows. A first composition A was provided as in the reference example, with the only difference that the perfume concentration was changed from 4 +/- 0.5 to 5.5 +/- 0.5. A second composition B was provided as in the reference example, with the only difference that the perfume concentration was changed from 4 +/- 0.5 to 2.5 +/- 0.5. As in the comparative example, the compositions were each mixed. The mixture was then extruded into a coaxial strand with composition A as the inner strand and composition B as the outer strand. An extruder was used for this. The coaxial, cylindrical strands had an outer diameter of 20.5 mm and an inner strand diameter of 7.3 mm. The strand was cut into 26.36mm long cylinders, each cylinder being formed into a ball. The final diameter of each ball was 25.4 mm.

Comparison experiments

Balls from the example and from the comparative example were used in identical toilet baskets and each flushed in a test chamber. The test chambers have an identical structure and are separated from each other so that there is no air exchange between the chambers. Each test chamber also has a toilet bowl and is flushed by a constant air flow. The test chamber is located in a room (measuring room) specially set up for the test chamber, which is odorless, can be well ventilated and, if necessary, can be forcibly ventilated using an activated carbon filter. The volume fraction of carbon dioxide in the measuring room is less than 0.15 vol.-%, the air exchange rate of the chamber is at least 4.4 m ³ /h per Person. The temperature in the measuring room is 20 °C and is constant during the measurement. The measuring room is not exposed to direct sunlight and other disturbing light and noise sources have been minimized as much as possible. All devices belonging to the test chamber must be odorless. The evaluation of the odor strength is carried out by at least 20 examiners, usually using an equal number of men and women who have been trained in smell and who are all at least 16 years old. At the time of evaluating the compounds, the examiners are not influenced by disruptive factors such as contact with perfumes, food, other stimulants or even colds or allergies.

The toilet baskets were hung in the toilet bowls in identical positions, and each toilet bowl was flushed once per hour. Each rinse used 6 L of water. The measurements were taken by the investigators at 4, 72, 96, 120, 144, 168 and 172 hours. For the evaluation, the examiner opens the window, positions his head inside the test chamber, carries out the smell test, pulls his head out again and then closes the window.

The examiners had a clear impression that the fragrance strength of the example according to the invention was greater than that of the comparative example. The consumer notices that after just 72 hours the scent impression has increased compared to the comparison example. Since the core was exposed, the initial difference to the comparative example was small; only a loss of 24% was taken by the consumer at the beginning, but this was surprisingly quickly made up. Surprisingly, the consumer results show that the toilet blocks and toilet baskets according to the invention give off a stronger scent impression over the entire period of use than the reference, even though the amount of perfume used is identical.

The essential part of the method according to the invention is, in cross section, in Fig.5 shown. A co-extruded strand section 7 is placed in a press 8. The final shape of the press 8 is a ball, with the same volume as the strand section 7. Because the troughs of the press 8 are brought together and the final shape is thus achieved, the strand section is deformed into a ball according to the invention.

An exemplary toilet basket that conforms to the invention is shown in Fig. 6 shown. In Fig. 6 3 toilet blocks are seen, each of which has a jacket 2 and a pole 3. The toilet blocks are shown in the toilet basket, which is shown in dashed lines with a hanger, from the front view. The basket is shown schematically so that the toilet blocks are easier to see. The toilet blocks are arranged irregularly to one another because each pole 4 points in a different direction.

Claims (14)

1. A device for a toilet bowl comprising:

   - at least two, preferably at least three, toilet rim blocks (1), which each consist of at least one shell (2) and one core (3),

   wherein the shell (2) comprises a first composition and the core (3) comprises a second composition,

   wherein the first and the second composition preferably differ by at least one of the following features: different active ingredients, different concentration of the same active ingredient, different viscosity;

   wherein the shell (2) surrounds the core (3) in part,

   wherein the core (3) projects, on at least one side of the toilet rim block, in the form of a pole (4), up to the surface and is exposed in the process,

   - means for holding the toilet rim block on the toilet bowl,

   wherein the toilet rim blocks (1) are arranged so as to be irregular with respect to one another by at least one pole (4, 5),

   wherein the toilet rim blocks (1) are spherical,

   wherein the toilet rim blocks (1) are produced by a production method,

   wherein a co-extruded strand portion (7) is placed in a press (8),

   wherein the final shape of the press (8) is a sphere, the volume of which is identical to that of the strand portion (7),

   wherein cavities of the press (8) are brought together and the final shape is thus achieved,

   wherein the strand portion (7) is deformed to form a sphere.
2. The device according to claim 1, wherein the profile of the core (3) is such that the surface of the exposed face changes with uniform wear of the surface of the toilet rim block (1).
3. The device according to at least one of the preceding claims, wherein the surface of the exposed face of the core (3) increases with uniform wear of the surface of the toilet rim block (1).
4. The device according to at least one of claims 1-2, wherein the surface of the exposed face of the core (3) reduces with uniform wear of the surface of the toilet rim block (1).
5. The device according to claim 4, wherein, for the undissolved toilet rim block (1), the area ratio of the exposed surface of the core (3) to the exposed surface of the shell (2) is between 5% and 67%, more preferably between 10% and 38%.
6. The device according to claim 4 and/or claim 5, wherein, when the toilet rim block (1) has been partially used, the area ratio of the exposed surface of the core (3) to the exposed surface of the shell (2) is between 1:3 and 1:1.
7. The device according to at least one of the preceding claims, wherein at least one portion, preferably the central portion, of the core (3) is in the form of a cylindrical segment (6).
8. The device according to at least one of the preceding claims, comprising a second pole (5) which, on the side of the toilet rim block (1) opposite the first pole (4), projects to the surface and is exposed in the process.
9. The device according to at least one of the preceding claims, wherein the first pole (4) and the second pole (5) are connected by a strand-like core (3).
10. The device according to at least one of the preceding claims 8-9, wherein the cross-sectional profile of the core (3) has a cross-sectional reduction between the first pole (4) and the second pole (5).
11. The device according to at least one of the preceding claims 8-9, wherein the cross-sectional profile of the core (3) has a cross-sectional enlargement between the first pole (4) and the second pole (5).
12. The device according to at least one of the preceding claims, wherein the shell (2) annularly surrounds the core (3).
13. The device according to at least one of the preceding claims, wherein the first and the second composition differ by a different concentration of the same active ingredient, wherein the core (3) has a concentration of an active ingredient which is at least 0.5 wt.% higher, preferably at least 1 wt.% to 10 wt.% higher.
14. The device according to at least one of the preceding claims, wherein the device is a rim block cage comprising a receptacle, which can be arranged in the toilet bowl, for the at least two toilet rim blocks (1).

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